Manufacture of cast phenolic resin



Patented Mar. 25, 1947 MANUFACTURE OF CAST PHENOLIC RESIN Charles S. Webber, Loudonville, N. Y., and

Stewart B. Luce and Frederick M. Murdock, assignors to Monsanto Chemical Company, St. Louis, Mo., a corpora- Springfield, Mass.,

tion of Delaware No Drawing. Original application March 31, 1039, Serial No. 265,344. Divided and this application April 6, 1943, Serial No. 481,996

18 Claims. 1

Our present invention has to do with the manufacture of cast phenolic resins made by the condensation of phenol and formaldehyde. In accordance with one process of manufacture phenol and formaldehyde have been reacted in the presence of soda ash or other suitable alkali and lactic acid and after the reaction is complete, the resin has been dehydrated by boiling under vacuum until it is substantially free from water. The mix is then acidified by the addition of lactic acid in excess of the equivalent of the alkali after which the mixture is heated'further.

A softener, ordinarily glycerine, is then added,

the material is boiled down and thickened until the desired viscosity is reached and it is cast and hardened in the usual manner. Resins made in this way with glycerine as a softener tend to absorb water to some extent and may blister on prolonged exposure to hot or cold water. Their impact strength is less than is desirable and the material is relatively hard to work and brittle.

We have discovered that it is possible to reduce the tendency to water absorption by two-thirds and the tendency to blister on the exposure to either hot or cold water; also, that the impact strength can be increased from 50 to 125 percent, the working of the material made easier, the resin made tougher and the hardness increased so that it is less likely to scratch. These important and useful results are accomplished by using what we term a phenolic softener alone or in combination with certain other materials as, for instance. methyl (or ethyl) phthalyl ethyl glycollate, these substances being usually added to the mix after the initial reaction, the dehydration, and the acidification have been performed, although it is possible to produce a similar result if proper additions to the mix during the alkaline reaction stage are made under conditions such that there will remain in the mix after neutralization phenol or a proper derivative thereof with formaldehyde.

In the following description the word phenol is intended to denominate a substance having a formula CsHsOH, but it will be apparent to those skilled in the art that other phenols or equivalent substances may be employed in certain circumstance:

The phenolic material used as a softener may be either unreacted phenol or soluble fusible phenolic resinsof the Novolak type. See Ellis, The Chemistry of Synthetic Resins.)

In practicing our improved process, we proceed in general as had been done heretofore in the manufacture of cast phenolic resins in which glycerine has been employed as a softener. This procedure is conveniently referred to as comprising seven steps or stages; (1) initial reaction of the materials under alkaline conditions, (2) dehydration by heating in a vacuum, (3) acidification, (4) addition of the softener, (5) thickening by boiling, (6) casting, (7) curing.

A procedure will now be described for making a cast phenolic resin embodying our invention where perfect clarity is not required but maximum strength and workability are desirable.

Stage 1. Initial reaction-The following materials are mixed and placed in a suitable vacuum kettle.

Parts by weight Phenol 100 Formaldehyde (37% solution) 258 Soda ash 5' Lactic acid (50% solution) 1.7

These are reacted for 2 /2 hours at C., with stirring and under a vacuum of 20 to 22 inches of mercury. This degree of vacuum does not distill off any appreciable amount of the reactants but does prevent air from coming in contact with the mix thus preventing discoloration.

Stage 2. Dehydration.-The resin is then boiled under a higher vacuum starting from 25 or 26 inches and ending at from 28 to 29 inches. The temperature is maintained at 50 C., throughout the period and heating is carried on from 3 to 6 hours depending on the size of the batch and the efficiency of the condensers.

Stage 3. Acidification.-After the resin has been sufficiently dehydrated the temperature is raised to 65 C., while still under the high vacuum and 19.5 parts of 50% solution of lactic acid is added.

This is a 25% excess over the equivalent theoretically required to neutralize the soda ash. Heating is continued at 65 for fifteen minutes under the same vacuum and approximately 200 parts of base resin containing about 10% of water is produced.

Up to this point the process is in accordance with common procedure and produces what is preferred to hereafter as the base or intermediate resin.

Stage 4. Addition of the softener.-If the regular procedure were adhered to, glycerine would then be added, the resin would be heated until the desired viscosity is reached and then cast and hardened in the usual manner. Such a resin as already pointed out is deficient in certain respects which it is the object of the present in-,

vention to improve. In accordance with the present invention, several possible addition agents or combinations of addition agents may now be added to give to the resulting product the desired physical properties.

Example A. Phenol-To 100 parts of the base resin prepared as described above 4 to 12 parts of unreacted phenol may be added, the resin thickened under the vacuum, and then cast and cured in the usual manner. When 8 parts of phenol are used, which is the amount preferred, the resulting product is more hazy than when glycerine is used but the water absorption of the resin is reduced about two-thirds, the tendency to blister on exposure to hot or cold water is reduced, the impact strength is increased about 50%, the working of the material is made easier, and the resin is tougher and it is less likely to scratch.

Example B. Phenol plus methyl phthalyl cthyl glycollate.-To 100 parts of the base or intermediate resin prepared as described above 4 to 12 parts of phenol, preferably 8 parts, and from 3 to parts of methyl phthalyl ethyl glycollate, preferably 4 parts, are added and the resin completed, cast and curedas usual. This product is clearer than when phenol alone is used and has the other advantages derived from the use of phenol.

Example C. Phenol and formaldehyde.'To 100 parts of the intermediate resin are added from 4 to 12 parts of phenol, preferably 8 parts, and from 5 to 14 parts of 37% formaldehyde solution. When added at this stage, the additional phenol and formaldehyde react under acid conditions, the batch having been already acidifiedand, therefore, we believe tend to form an acid condensed resin similar to Novolak which, in the case where a molar deficiency of formaldehyde is used, may be true Novolak. The batch is completed as already described. This product is slightly more hazy than the preceding but the impact strength is increased from 100 to 125%. Larger amounts of formaldehyde seem to improve the clarity without perceptible decrease in strength.

Example D. A phenolic compound of the Novolalc type.To 100 parts of the base or intermediate resin are added parts of a phenolic compound of the Novolak type, this Novolak made as follows:

' Parts Phenol 100 Formaldehyde (37% solution) 65 Phthalic anhydride 5 are refluxed under a water cooled condenser until the mix becomes turbid by the separation of water. The mixture is then dehydrated until clear, either by vacuum distillation or by boiling in the open. The resulting product is a phenolic resin of the Novolak type. This Novolak resin may be added to the base resin as a softener, after which the resin is finished in the usual manner. The resulting resin is similar in its physical properties to that made with phenol plus methyl phthalyl ethyl glycollate but has somewhat more haze.

Example E. A phenolic compound of the Novolalc type with methyl phthalyl ethyl glycollate- 10 parts of the phenolic compound of the Novolak' type described in the recedin example and from 3 to 8 parts of methyl phthalyl ethyl glycollate are added to 100 parts of the base or intermediate resin and the resin completed as described. The clarity of this resin is superior to the clarity of the preceding resin. The other properties are about the same.

Example F. A phenolic compound of the N0120- lalc type added after the initial reaction.--We have also found that it is possible to obtain similar results by adding a proper amount of the phenolic resin of the Novolak type (made as described in Example D) to the mix at the end of the initial reaction (Stage 1) and before dehydration (Stage 2). An example of this procedure is as follows:

10 parts of the phenolic compound of the Novolak type made as previously described is added to parts of the base resin immediately after the condensation reaction has been carried on at 65 C. for 2%; hours. After acidification 4 parts of methyl phthalyl ethyl glycollate are added as this assists in reducing the haze. The resulting product has an increase in breaking strength of about and the time necessary for curing it is decreased about 25%. More than 10 parts of the phenolic compound of the Novolak type may be added but in that case the increase in impact strength is only from 40 to 50%.

The methyl phthayl glycollate acts as a clarifying' agent. Other similar esters of glycollic acid, such as ethyl phthalyl ethy1 glycollate may be employed provided they are soluble in the cast phenolic resin. The preferred glycollates are esters of phthalyl glycollic acid made from an alcohol with not more than three carbon atoms. Butyl phthalyl butyl glycollate is insoluble and, therefore, is not suitable.' These materials tend to clarify the resin and reduce the haze whether used in conjunction with phenol, or with a phenolic compound of the Novolak type or alone.

This application is a division of our co-pending application Serial No. 265,344, filed March 31, 1939, now Patent No; 2,321,783.

We claim:

1. In the method of making cast phenolic resins, the steps which comprise reacting substantially one molecular proportion of phenol with substantially three molecular proportions of formaldehyde in a weakly alkaline condition, partially dehydrating the initial reaction product under reduced pressure, acidifying the liquid reaction mixture by the addition of lactic acid and increasing the toughness and workability of the cured resin while maintaining hardness and high water resistance by combining with the liquid reaction mixture phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, thickening the resin so formed by dehydration under reduced pressure, pouring into a mold and curing by heating.

2. A cast phenol formaldehyde resin prepared by reacting substantially one molecular proportion of phenol with substantially three molecular proportions of formaldehyde in a weakly alkaline condition,"partially dehydrating the initial reaction product under reduced pressure, acidifying the liquid reaction mixture by the addition of lactic acid, increasing the toughness and workability of the cured resin while maintaining hardness and water resistance by combining with the liquid reaction mixture phenol reacted with formaldehyde to form a resin of the Novolak tyDein the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, thickening the resin so formed by dehydration under reduced pressure, pouring into a mold and curing by heating. 1

3. In the method of making cast phenolic resins which comprises reacting substantiallyone molecular proportion of phenol with a large excess over one molecular proportion of formaldehyde under alkaline conditions, acidifying, pouring into a mold and hardening by heating, the

step which comprises adding phenol reacted with formaldehyde to form a resin of the Novolak type to the reaction'mixture at a point subsequent to the initial reaction between the phenol and formaldehydebut prior to pouring into the mold, the Novolak being added in the proportion of 20 parts for every 100 parts of phenol in the original reaction mixture. I

4. In the method of making cast phenolic resins which comprises reacting substantially one molecular proportion of phenol with substantially three molecular proportions of formaldehyde in a weakly alkaline condition, acidifying, pouring into a mold and hardening by heating, the step which comprises adding phenol reacted with formaldehyde to form a resin of the Novolak type at a point subsequent to the initial reaction between the phenol and formaldehyde but prior to pouring into the mold, the Novolak being added in the proportion of 20 parts for every 100 parts of phenol in the original reaction mixture.

5. A cast phenol formaldehyde resin prepared by reacting substantially one molecular propor-' tion of phenol with a large excess over one molecular proportion of formaldehyde under alkaline conditions, acidifying, pouring into a mold and hardening by heating, to which has been added, at a point subsequent to the initial'reaction between the phenol and formaldehyde bpt prior to pouring into the mold, phenol reacted 'with formaldehyde to form a resin of the Novalak type in the proportion of 20 parts of Novolak] for every 100 parts of phenol in the original reaction mixture.

'6. A cast phenol formaldehyd resin prepared by reacting substantially one molecular proportion of phenol with substantially three molecular proportions of formaldehyde under alkaline conditions, acidifying, pouring into a mold and hardening by heating to which has been added at a point subsequent to the initial reaction between the phenol and formaldehyde, phenol reacted with formaldehyde but prior to pouring into the mold to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture.

7. In the method of making cast phenolic resins, the steps which comprise reacting substantially 1 molecular proportion of phenol with a large excess over 1 molecular proportion of formaldehyd under alkaline conditions, acidifying the liquid reaction mixture, adding phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for very 100 parts of phenol in the original reaction mixture, pouring into a mold and hardening by heating.

8. In the method of making cast phenolic resins, th st ps which comprise reacting substantially 1 molecular proportion of phenol with a large excess over 1 molecular proportion of formaldehyde under alkaline conditions, partially dehydrating the initial reaction product, acidifying the liquid reaction mixture, adding phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every parts of phenol in the original reaction mixture, pouring into a mold and hardening by heating.

'9. In the method of making cast phenolic resins. th steps 'hich comprise reacting substantially 1 molecular proportion'of phenol with a large excess over 1 molecular proportion of formaldehyde under alkaline conditions, partially dehydrating the initial reaction product under reduced pressure, acidifying the liquid reaction mixture. adding phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, pouring into a mold and hardening by heating.

10. In the method of making cast phenolic resins, the steps which comprise reacting substantially 1 molecular proportion of phenol with substantially 3 molecular proportions of formalde- .hyde in a weakly alkaline condition, acidifying reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, pouring into a mold and hardening/by heating.

12. In the method'of making castphenolic resins, the steps which comprise reacting substantially 1 molecular proportion of phenol with substantially 3 molecular proportions of formaldehyde under weakly alkaline conditions partially dehydrating the initial reaction product under reduced pressure, acidifying the liquid reaction mixture, adding phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, pouring into a mold and hardening by heating.

13. A cast phenol formaldehyde resin, prepared by reacting substantially 1 molecular proportion of phenol with a large excess over 1 molecular proportion of formaldehyde under alkaline conditions, acidifying the liquid reaction mixture, adding phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, pouring into a mold and hardening by heating.

14. A cast phenol formaldehyde resin, prepared by reacting substantially 1 molecular proportion of phenol with a large excess over 1 molecular proportion of formaldehyde under alkaline conditions, partially dehydrating the initial reaction product, acidifying the liquid reaction mixture, adding phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, pouring into a mold and hardening by heating.

15. A cast phenol formaldehyde resin, prepared by reacting substantially 1 molecular proportion of phenol with a large excess over 1 molecular proportion of formaldehyde under alkaline conditlons, partially dehydrating the initial reaction product under reduced pressure, acidifying the liquid reaction mixture, adding phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, pouring into a mold and hardening by heating.

16. Aicast phenol formaldehyde resin, prepared by reacting substantially 1 molecular proportion of phenol with substantially 3 molecular proportions of formaldehyde under alkaline conditions, acidifying the liquid reaction mixture, adding phenol reacted with formaldehyde to form a resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, pouring into a mold and hardening by heating.

1'7. A cast phenol formaldehyde resin, prepared by reacting substantially 1 molecular proportion of phenol with substantially 3 molecular proportions of formaldehyde under alkaline conditions, partially dehydrating the initial reaction product, acidifying the liquid reaction mixture, adding phenol reacted with formaldehyde to form a. resin of the Novolak type in the proportion of 20 parts of Novolak for every 100 parts of phenol in the original reaction mixture, pouring into a. mold and hardening by heating.

CHARLES S. WEBBER. STEWART B. LUCE. FREDERICK M. MURDOCK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,168,981 Flood et a1 Aug. 8, 1939 2,321,783 Webber et a1 June 15, 1943 2,073,938 Kyrides Mar, 16, 1937 1,909,786 Pantke May 16, 1933 

